Friction modifiers and antiwear additives for fuels and lubricants

ABSTRACT

The invention relates to lubricant and fuel additives having antiwear and friction reducing properties. The invention also relates to compositions of oils with viscosities appropriate for lubricants, greases produced therefrom, and fuels and methods for making these compositions. Described in this invention are products of nitrogen heterocycles, such as benzotriazole and tolyltriazole, with amines, such as alkyl amines, aliphatic diamines, alicyclic amines, heterocyclic amines, propylene amines, and aliphatic etheramines, that are linked using carbonyl compounds (e.g., aldehyde, ketone or glyoxal). Additionally, products generated by the reaction of carboxylic acids or carboxylic acid generating compounds (e.g., salts or esters) with carbonyl (e.g., aldehyde, ketone or glyoxal) coupled nitrogen heterocycles and amines, including those described above, are also included in this invention. These products can be used in fuels and lubricants to produce improved antiwear and friction reducing properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 08/245,275, filed on May 18,1994, now U.S. Pat. No. 5,482,521.

FIELD OF THE INVENTION

The invention relates to lubricant and fuel additives having antiwearand friction reducing properties. The invention also relates tocompositions of oils with viscosities appropriate for lubricants,greases produced therefrom, as well as fuels and methods for makingthese compositions.

BACKGROUND OF THE INVENTION

Tolyltriazole and alkyl amines linked by formaldehyde are known toprovide antiwear properties in fuels and lubricants. Katritzky, Fan, andFu (Alan R. Katritzky, Wei-Qiang Fan, and Cong Fu, J. Org. Chem., 1990,55, 3209-3213) describe syntheses in which a nitrogen heterocycle,benzotriazole, is linked to primary and/or secondary amines usingglyoxal.

SUMMARY OF THE INVENTION

This invention includes products of nitrogen heterocycles, such asbenzotriazole and tolyltriazole, with amines, such as alkyl amines,aliphatic diamines, alicyclic amines, heterocyclic amines, propyleneamines and aliphatic etheramines, that are linked using carbonylcompounds (e.g., aldehyde, ketone or glyoxal). Whereas some of theproducts themselves may be related to Katritzky, Fan, and Fu's work, thefuel and lubricant compositions of these products and the unexpected butexcellent antiwear and friction reducing properties of thesecompositions are unique. These remarkable benefits are expected for avariety of fuel compositions and for a variety of synthetic, mineraloil, and vegetable oil based lubricants. Additionally, other additivesgenerated by the reaction of carboxylic acids or carboxylic acidgenerating compounds (e.g., salts or esters) with carbonyl (e.g.,aldehyde, ketone or glyoxal) coupled nitrogen heterocycles and amines,including those described above, can be used in fuels and lubricants toproduce improved antiwear and friction reducing properties. In additionto antiwear and friction reducing properties, antioxidant, hightemperature stabilizing, anticorrosion, antistaining, metaldeactivation, cleanliness, detergency/dispersancy, antifatigue, extremepressure, and demulsifying/emulsifying properties are likely with manyof the embodiments of this invention.

One embodiment of this invention is a compound comprising the reactionproduct of at least one nitrogen heterocycle, at least one amine, atleast one carbonyl compound, and, optionally, at least one carboxylcompound.

Another embodiment is a lubricant or fuel additive comprising thereaction product of at least one nitrogen heterocycle, such astolyltriazole, at least one amine, and at least one glyoxal.

Yet another embodiment of this invention is a lubricant or a fuelcomposition comprising a major amount of oil with viscosity suitable foruse as a lubricant, grease produced therefrom, or a fuel and a minoramount of an additive comprising the reaction product of at least onenitrogen heterocycle, at least one amine, and at least one glyoxal.

A further embodiment of this invention is a lubricant or a fuelcomposition comprising a major amount of oil with viscosity suitable foruse as a lubricant, grease produced therefrom, or a fuel and a minoramount of an additive comprising the reaction product of at least onenitrogen heterocycle, at least one amine, at least one carbonylcompound, and, optionally, at least one carboxyl compound or carboxylgenerating compound.

Another embodiment of this invention is a method of making a lubricantor a fuel comprising incorporating a major amount of oil with viscositysuitable for use as a lubricant, grease produced therefrom, or a fuelwith a minor amount of an additive comprising the reaction product of atleast one nitrogen heterocycle, at least one amine, and at least onecarbonyl, such as glyoxal. An optional variation of this embodiment isone in which at least one carboxyl compound is included in the reactionproduct.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention is directed to additives which are soluble infuels or lubricants; less soluble embodiments can be used in greases orother solid lubricants. An additive has been discovered which hasimproved antiwear and friction reducing properties when incorporatedinto lubricating oils and fuels comprising the reaction product of acarbonyl, such as glyoxal, a nitrogen heterocycle and an amine selectedfrom the group consisting of an alkyl amine, aliphatic diamine,alicyclic amine, heterocyclic amine, propylene amine and aliphaticetheramine. A carboxylic acid or a carboxylate forming compound may bealso included in the reaction product.

One embodiment of this invention is a compound comprising the reactionproduct of at least one nitrogen heterocycle, at least one amine, atleast one carbonyl compound, and at least one carboxyl compound.

An additional embodiment of this invention is a compound comprising thereaction product of at least one nitrogen heterocycle, such astolyltriazole, at least one amine, and at least one glyoxal.

Another embodiment of this invention is a lubricant or a fuelcomposition comprising a major amount of oil with viscosity suitable foruse as a lubricant, grease produced therefrom, or a fuel and a minoramount of an additive comprising the reaction product of at least onenitrogen heterocycle, at least one amine, and at least one glyoxal.

Yet another embodiment of this invention is a lubricant or a fuelcomposition comprising a major amount of oil with viscosity suitable foruse as a lubricant, grease produced therefrom, or a fuel and a minoramount of an additive comprising the reaction product of at least onenitrogen heterocycle, at least one amine, at least one carbonylcompound, and at least one carboxyl compound or carboxyl generatingcompound.

Another embodiment of this invention is a method of making a lubricantor a fuel comprising blending a major amount of oil with viscositysuitable for use as a lubricant, grease produced therefrom, or a fuelwith a minor amount of an additive comprising the reaction product of atleast one nitrogen heterocycle, at least one amine, and at least onecarbonyl, such as glyoxal. A variation of this embodiment is one inwhich at least one carboxyl compound is included in the reactionproduct.

The nitrogen heterocycle is a 5-membered ring structure in which threeof the ring members are nitrogen, the other ring members can be oxygen,sulfur or carbon atoms. Typical nitrogen heterocycles are triazoles,especially those already known for their antioxidant characteristics.The triazole is characterized by the following structural formula:##STR1## where R₁ is hydrogen or an alkyl group containing 1 to 60carbon atoms or an alkyl group containing 2 to 60 carbon atoms and atleast one heteroatom which is oxygen, sulfur, nitrogen and combinationsthereof. Representative examples of alkyl groups include methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl,polyisobutyl, polyisobutenyl, oligomeric decene, and polyisopropylene orany combination thereof. Non-limiting examples of suitable triazolesinclude tolyltriazole, where R₁ is methyl, ethylbenzotriazole,propylbenzotriazole, butylbenzotriazole, the higher benzotriazoles suchas dodecylbenzotriazole and oxygenated benzotriazoles such ascarboxymethylbenzotriazole. The triazoles are known in the art and canbe obtained from commercial sources.

The carbonyl compound can be any compound containing the group (C═O)which occurs in aldehydes and ketones. This compound can becharacterized by the structural formula ##STR2## in which R₂ and R₃independently are hydrogen or linear, branched or cyclic hydrocarbyl orhydrocarbylene generally containing 1 to 200 carbon atoms, specifically1 to 60 carbon atoms, which are alkyl, aryl, arylalkyl or alkylaryl. Thehydrocarbyl or hydrocarbylene group can also generally contain 2 to 200carbon atoms, specifically 2 to 60 carbon atoms, and at least oneheteroatom which can be oxygen, sulfur or nitrogen. Non-limitingexamples of typical carbonyl compounds include formaldehyde,heptaldehyde, hexaldehyde, acetaldehyde, propionaldehyde,paraformaldehyde, benzaldehyde, salicylaldehyde, acetone, diethylketone, methyl ethyl ketone and 2-ethylhexanal. Also included in thisdefinition and useful in this invention are dicarbonyl compounds,including dialdehydes, such as glutaraldehyde. These compounds are knownin the art and are readily available from commercial sources or areeasily made using known methods.

The carbonyl compound may also be a glyoxal which may be characterizedby the formula

    R.sub.2 COR.sub.3 CO

where R₂ and R₃ are as defined above. One commercially available form isglyoxal.

The nitrogen heterocycle and the carbonyl compound are reacted with atleast one amine which can be an alkyl amine, long-chain aliphatic amine,branched chain aliphatic amine, alicyclic amine, heterocyclic amine,aliphatic diamine, aliphatic triamine, propylene amine, oxygenatedamine, aliphatic etheramine, ether diamine, polyether primary amine,hydroxyl-containing amine and mixtures thereof.

Also polyethylene amines such as ethylene diamine, diethylene triamine,triethylene tetramine, tetraethylene pentamine and mixtures thereof,higher oligomers thereof, hydrocarbyl substituted polyethylene amine,and all of the corresponding polypropylene amines and polybutyleneamines and their homologues and mixtures may be used.

The alkyl amines are amines designated by the following structure:

    R.sub.4 NR.sub.5 R.sub.6

in which R₄, R₅ or R₆ is, independently, a hydrogen atom in the case ofa primary or secondary amine, or R₄, R₅ and R₆ are the same or differenthydrocarbon groups, and where at least one of R₄, R₅ or R₆ must behydrogen. R₄, R₅ or R₆ is generally a hydrocarbyl or hydrocarbylenegroup generally containing 1 to 200 carbon atoms, specifically 1 to 60carbon atoms and can contain at least one heteroatom which is oxygen,sulfur, nitrogen and combinations thereof, and, generally, 2 to 200carbon atoms, specifically 2 to 60 carbon atoms. Non-limiting examplesof the alkyl amines include the straight chain monoamines such as methylethyl amine, propylamine or butylamine. The particularly preferredamines are the long-chain aliphatic amines such as pentylamine,hexylamine, octylamine, dioctylamine, dicocoamine, dioleylamine and thelike. The term "long chain" designates the amines containing hydrocarbylgroups of C₅ and higher, preferably over C₈ and in the range of C₅ toC₂₂ or more, preferably C₈ to C₂₀. The branched chain amines include,but are not limited to, the short chain amines, i.e., isopropylamine,isobutylamine, diisobutylamine and longer chain branched amines such as2-ethylhexylamine and bis(2-ethylhexyl)amine. The term "short chainamines" designates amines containing hydrocarbon groups of C₅ and lower,preferably C₃ and lower.

Non-limiting examples of the alicyclic amines are dicyclohexylamine,1,4-diaminocyclohexane, piperidine and hexamethyleneimine.

The contemplated amines are also heterocyclic in which the nitrogen atomis an integral member of a ring structure which is predominantlycomposed of carbon atoms. Suitable, but not limiting examples ofheterocyclic amines include morpholine, aminopropylmorpholine (APM) andaminoethylpiperazine (AEP).

The aliphatic diamines are also used. In general the long-chain diaminesare contemplated and have the structural formula: ##STR3## where R₇ isan alkylene group containing 10 to 30 carbon atoms and R₈ is an alkylenegroup containing 2 to 4 carbon atoms. Some non-limiting examples ofdiamines include N-tallow-1,3-propylenediamine,N-oleyl-1,3-propylenediamine, N-linoleyl-1,3-propylenediamine,N-stearyl-1,3-propylenediamine, N-soya-1,3-propylenediamine,N-cocoyl-1,3-diaminopropane, N-oleyl-1,3-diaminopropane,N-isostearyl-1,3-propylenediamine, N-tallow-1,2-ethylenediamine,N-oleyl-1,2-ethylenediamine, N-linoleyl-1,2-ethylenediamine,N-stearyl-1,2-ethylenediamine, N-soya-1,2-ethylenediamine,N-cocoyl-1,2-diaminoethane, N-oleyl-1,2-diaminoethane,N-isostearyl-1,2-ethylenediamine, and mixtures of two or more of theseamines.

Aliphatic triamines may also be used. In general, aliphatic triamineshaving the following formula are contemplated:

    R.sub.9 NH(CH.sub.2 CH.sub.2 CH.sub.2)NH(CH.sub.2 CH.sub.2 CH.sub.2)NH.sub.2

where R₉ is selected from hydrogen or C₁ -C₂₀ linear, branched, orcyclic hydrocarbyl or hydrocarbylene group. The hydrocarbyl orhydrocarbylene group can also contain 2 to 20 carbon atoms and at leastone heteroatom which can be oxygen, sulfur, nitrogen, and combinationsthereof. Non-limiting examples of these amines include diethylenetriamine, triamino propane, N,N'-di(2-aminoethyl)-amine,bis(hexamethylene) triamine, pentamethyl diethylenetriamine,2,2-dimethyldiethylenetriamine, N1-tert. butyl-1,2,3-triaminopropane,2,2,5,5-tetramethyl diethylenetriamine, 1,3,6-triaminomethylhexane,1,2,3-triaminoethylpropane, 4-aminomethyl-octamethylenediamine,3,3'-diamino-dipropylamine, spermidine, 4,4'-diamino-dibutylamine,6,6'diaminohexylamine, 2,4-bis(4-aminocyclohexylmethyl)cyclohexylamine.

Propylene amines may also be used. These amines are typified by thefollowing structure:

    R.sub.10 NR.sub.11 (CH.sub.2 CH.sub.2 CH.sub.2 NH).sub.x CH.sub.2 CH.sub.2 CH.sub.2 NR.sub.12 R.sub.13

where x is 0 to 10, and R₁₀, R₁₁, R₁₂, and R₁₃ are independentlyselected from hydrogen, or generally C₁ -C₂₀₀, specifically C₁ -C₆₀linear, branched or cyclic hydrocarbyl or hydrocarbylene. Thehydrocarbyl or hydrocarbylene group can also generally contain 2 to 200carbon atoms, specifically 2 to 60 carbon atoms, and at least oneheteroatom which can be oxygen, sulfur, nitrogen, and combinationsthereof.

The oxygenated amines are also suitable. The oxygenated aminescontemplated include the aliphatic etheramines such as thealkoxypropylamines having the structural formula

    R.sub.14 .paren open-st.O--(C.sub.3 H.sub.6)).sub.a --NH.sub.2

where a is 1 to 20 and in which R₁₄ is an alkyl group which contains 4to 20 carbon atoms, preferably 6 to 18 carbon atoms. Non-limitingexamples of the alkoxypropylamines include 3-methoxypropylamine,3-ethoxypropylamine, 3-propyloxypropylamine, 3-butyloxy-propylamine,3-octyloxypropylamine, 3-hexoxypropylamine, 3-heptoxypropylamine,3-nonyloxypropylamine and 3-decyloxypropylamine.

The ether diamines are another class of oxygenated amines which aresuitable. Non-limiting examples of the ether diamines are those havingthe structure: ##STR4## Where a is 1 to 20 and R₁₄ is as defined above,but where R₁₄ preferably contains 6 to 18 carbon atoms arranged in astraight or branched chain configuration. R₁₅ is an alkyl groupcontaining 2 to 4 carbon atoms, R₁₆ is an alkyl group having at least 2to 3 carbon atoms, at most 5 to 10 carbon atoms. Non-limiting examplesof ether diamines include hexoxypropyl-1,3-propylenediamine,heptoxypropyl-1,3-propylenediamine, octoxypropyl-1,3-propylenediamineand nonoxypropyl-1,3-propylenediamine and any mixtures of the foregoingether diamines.

The polyether primary amines are also contemplated. Suitable polyetherprimary amines have the following structural formula

    R.sub.17 --O(C.sub.2 H.sub.3 (R.sub.18)O).sub.n C.sub.3 H.sub.6 NH.sub.2

where R₁₇ is an alkyl-substituted phenyl group containing 14 to 26carbon atoms, C₆ to C₃₀ alkyl group or C₇ to C₃₀ aralkyl group, n is aninteger ranging from 2 to 10 and R₁₈ is independently hydrogen ormethyl. These alkyl-substituted phenol-derived polyetheramines are soldby Texaco Chemical Co. under the trademark Surfonamine. Those availablecommercially include:

    ______________________________________                                        Trademark       Structure                                                     ______________________________________                                        Surfonamine MNPA-380                                                                          nonylphenyl-1EO--2PO--NH.sub.2                                Surfonamine MNPA-510                                                                          nonylphenyl-4EO--2PO--NH.sub.2                                Surfonamine MNPA-750                                                                          nonylphenyl-9.5EO--2PO--NH.sub.2                              Surfonamine MNPA-860                                                                          nonylphenyl-12EO--2PO--NH.sub.2                               ______________________________________                                    

Contemplated polyether primary amines are those derived from nonylphenolethoxylates such as where R₁₇ is nonylphenyl. Specific examples of thesepolyether primary amines include the compounds sold by Texaco under thetradename SURFONAMINE MNPA.

In general, hydroxyl-containing amines having the following formula arealso contemplated as oxygenated amines: ##STR5## where x and y areintegers from 1 to 10 and the sum of x+y is at least 1 and R₁₉ isselected from hydrogen or generally C₁ -C₂₀₀, specifically C₁ -C₆₀linear, branched, or cyclic hydrocarbyl or hydrocarbylene group, andwhere R₂₀ and R₂₁ are independently selected from C₂ -C₁₀ hydrocarbyleneoxide. The R₁₉ hydrocarbyl or hydrocarbylene group can also generallycontain 2 to 200 carbon atoms, specifically 2 to 60 carbon atoms, and atleast one heteroatom which can be oxygen, sulfur, nitrogen andcombinations thereof. Non-limiting examples of hydrocarbylene oxidesinclude ethylene oxide and styrene oxide.

The nitrogen heterocycle, the carbonyl compound and the amine can bereacted together in any sequence. However, for illustrative purposes,the carbonyl compound is added to a solvated mixture of the nitrogenheterocycle and the amine. The nitrogen heterocycle and the carbonylcompound are typically reacted in an equimolar proportion such that oneequivalent amount of the carbonyl compound is used for each equivalentamount of the nitrogen heterocycle and the amine. However, the inventionis also effective when the components are not added in equimolarproportions. In other words, an excess of any component may be added tothe reaction mixture without compromising the effectiveness of theinvention. The reaction is a condensation reaction in which water isformed as the product evolves. The amount of water produced by thereaction may be used to monitor the course of reaction: one mole ofwater is typically formed for each mole of product formed.

The reaction is carried out at a temperature of less than 50° C.,preferably less than 40° C., which increases to at least 60° C. to 70°C., at most 110° C. to 150° C. during the course of the reaction. Afterthe reactants have been contacted for at least 10 minutes to 1 hour,typically about 3 hours to about 48 hours, specifically about 6 hours toabout 24 hours, any solvent used to facilitate the reaction and anywater present which is produced by the reaction may be removed, usuallyby azeotropic and/or vacuum distillation. The solvent is not required tobe removed before use of these reaction products according to thisinvention. A solvent or diluent inert to the reactants can be used tofacilitate the reaction and which provide good solubility for thetriazole. Non-limiting examples of suitable solvents include methanol,ethanol, isopropyl alcohol, butanol and other similar alcohols. Aco-solvent may also be used. Non-limiting examples of co-solventsinclude toluene, benzene, xylene, hexane, cyclohexane and similarcompounds, and mixtures of similar compounds.

The reaction product is optionally treated with a carboxylic acid orcarboxylate forming compound, such as a salt or an ester of a carboxylicacid to form a further reaction product comprising partial, single ormultiple salts or covalent carboxylates or a mixture thereof. Carboxylicacids that may be used typically have the following structure: ##STR6##where R₂₂ is hydrogen or C₁ -C₃₀ linear, branched, aliphatic, aromatic,or alkylaromatic or cyclic hydrocarbyl or hydrocarbylene or a mixturethereof. The hydrocarbyl or hydrocarbylene group can also generallycontain 2 to 30 carbon atoms, and at least one heteroatom which can beoxygen, sulfur or nitrogen. Non-limiting examples of suitable carboxylicacids include oleyl, linoleic, dimer and sarcosine carboxylic acids.Non-limiting examples of suitable carboxylic acid forming compoundsinclude succinic, phthalic, trimellitic, benzene tetracarboxylic, andbenzophenone anhydrides. Linear or branched fatty acids are oftenpreferred.

As mentioned above, the nitrogen heterocycle, carbonyl, amine, andoptional carboxyl compounds may be reacted together in any order. Onepossible sequence is the combination of the nitrogen heterocycle,carbonyl, and amine group in any order, followed by the addition of thecarboxyl if desired.

Fuel and lubricant compositions containing additives made from the abovereaction products have improved antiwear and friction reducingproperties. It is believed that the nitrogen heterocycle, the amine, andthe carboxylate components (when present) provide the basis for thesynergistic friction reduction and antiwear properties provided by thesenovel additives.

All of the above described beneficial properties are believed to beenhanced as a result of this novel internal synergism. This uniquesynergism concept is believed to be applicable to similar structurescontaining single or multiple combinations of groups within the samemolecule including nitrogen heterocycles, amines, and, optionally,carboxylic acids. Products made according to this invention show goodstability and compatibility when used in the presence of other commonlyused additives in fuel and lubricant applications. Some products mayhave demulsive properties. Significant improvements in vehicle fueleconomy benefits and longer engine service lifetimes are expected. Withthe use of such additives in fuels, reduced pollution, as measured byhydrocarbon, carbon monoxide, and NO_(x) emissions, is also expected.

The reaction products are blended with lubricants in a concentration ofabout 0.01% to 10%, preferably, from 0.05% to 5% by weight of the totalcomposition.

As previously mentioned, the additives are suitable for use in engineoils and gear oils. The engine oils which will benefit from theseadditives include oils for gasoline and alternative fuel burning enginesand diesel engines. The contemplated gear oils which will benefit fromthe additives are hypoid gear oils which are exposed to the most severeservice conditions. Other gear oils contemplated include automotivespiral-bevel and worm gear axle oils.

Although the additives are successful in internal combustion engine oilsand gear oils, it is contemplated that the additives will successfullyperform in other functional fluids and industrial lubricants. Otherlubricant applications contemplated include the use of the instantadditives in circulation oils and steam turbine oils, gas turbine oils(both heavy-duty gas turbines and aircraft gas turbines), machine toollubricants and hydraulic fluids.

The contemplated lubricants are liquid oils in the form of either amineral oil or synthetic oil or mixtures thereof. Also contemplated aregreases in which any of the foregoing oils are employed as a base. Stillfurther materials which it is believed would benefit from the reactionproducts of the present invention are plastic materials.

In general, mineral oils, paraffinic, naphthenic, aromatic and mixturesthereof can be employed as a lubricating oil or as the grease vehicle.The lubricating oils can be of any suitable lubrication viscosity range,for example, from about 45 SSU at 100° F. to about 6000 SSU at 100° F.,and preferably from about 50 to 250 SSU at 210° F. Viscosity indexesrange from about 70 and higher, preferably 90 to 130. The averagemolecular weights of these oils can range from about 250 to about 800.

The additives of this invention are also effective in food-grade oils,such as vegetable oils or their derivatives.

It is also desirable to employ the additive in greases. The additive isparticularly useful when used in gear greases. However, other classes ofgreases which will benefit from the additive include greases forautomobile chassis lubrication, greases for journal and wheel bearings,etc. Typically, the range of application includes the automotiveindustry, railways and aviation industries.

Where the lubricant is employed as a grease, the lubricant is generallyused in an amount sufficient to balance the total grease composition,after accounting for the desired quantity of the thickening agent, andother additive components included in the grease formulation. A widevariety of materials can be employed as thickening or gelling agents.These can include any of the conventional metal salts or soaps, such ascalcium, or lithium stearates or hydroxystearates, which are dispersedin the lubricating vehicle in grease-forming quantities in amountssufficient to impart to the resulting grease composition the desiredconsistency. Other thickening agents that can be employed in the greaseformulation comprise the non-soap thickeners, such as surface-modifiedclays and silicas, aryl ureas, calcium complexes, and similar materials.In general, grease thickeners can be employed which do not melt ordissolve when used at the required temperature within a particularenvironment. However, in all other respects, any material which isnormally employed for thickening or gelling hydrocarbon fluids forforming greases can be used with the present invention.

Where synthetic oils, or synthetic oils employed as the vehicle for thegrease are desired in preference to mineral oils, or mixtures of mineraland synthetic oils are desired, various synthetic oils may be used.Typical synthetic oils include the polyalphaolefins, polypropyleneglycol, alkylated aromatics, such as alkylated naphthalenes,polyethylene glycol, trimethylol propane esters, neopentyl andpentaerythritol esters, di(2-ethylhexyl) sebacate, di(2-ethylhexyl)adipate, dibutyl phthalate, silicate esters, silanes, esters ofphosphorus-containing acids, hydrogenated synthetic oils, chain-typepolyphenyls, siloxanes and silicones (polysiloxanes) andalkyl-substituted diphenyl ethers typified by a butyl-substitutedbis(p-phenoxy phenyl) ether and phenoxy phenylethers.

The lubricating oils and greases contemplated for blending with thereaction product can also contain other additives generally employed inlubricating compositions such as corrosion inhibitors, detergents,dispersants, extreme pressure agents, viscosity index improvers,demulsifiers, friction reducers, antiwear agents and the like. Typicalexamples of these additives include but are not limited to phenates,metallic phenates, sulfonates, metallic sulfonates, imides, heterocycliccompounds, polymeric acrylates or esters or amides or succinimides,amines, amides, esters, sulfurized olefins or esters or amides orimides, succinimides, succinate esters, metallic or non-metallicphosphorodithioates, olefin copolymers, styrene-diene copolymers,methacrylates, organic borates, metallic detergents such as thosecontaining calcium or magnesium, arylamines, hindered phenols and thelike.

It is also contemplated that the additives are useful in fuels. Thefuels contemplated are liquid fuels, such as liquid hydrocarbon andliquid oxygenated fuels such as alcohols and ethers. The additivestypically can be blended in a concentration from about 1 to about 1,000pounds of additive per 1000 barrels of fuel, specifically about 25 toabout 500 pounds of additive per 1,000 barrels of fuel. Liquidhydrocarbon fuels include gasoline, kerosene, jet fuels, gas oils, fueloils, diesel oils and alcohol fuels which include methyl and ethylalcohols and ethers such as diisopropyl ether (DIPE), methyl tert-butylether (MTBE), ethyl tert-butyl ether (ETBE), tertiary amyl methyl ether(TAME), and mixtures of any or all of the above.

Specifically, the fuel compositions contemplated include gasoline basestocks such as a mixture of hydrocarbons boiling in the gasoline boilingrange which is from about 90° F. to about 450° F. This base fuel mayconsist of straight chains or branched chains, paraffins,cycloparaffins, olefins, aromatic hydrocarbons, or mixtures thereof. Thebase fuel can be derived from among others, straight run gasoline ornaphtha, alkylate, reformate, polymer gasoline, natural gasoline or fromcatalytically cracked or thermally cracked hydrocarbons catalyticallycracked reformed stock and mixtures thereof. The composition and octanelevel of the base fuel are not critical and any conventional motor fuelbase can be employed in the practice of this invention.

Further examples of fuels of this type are petroleum distillate fuelshaving an initial boiling point from about 75° F. to about 400° F. and afinal boiling point from about 250° F. to about 750° F. It should benoted in this respect that the term distillate fuels is not intended tobe restricted to straight-run distillate fractions. Non-limitingexamples of these distillate fuel oils include straight-run distillatefuel oils, alkylate, catalytically or thermally cracked (includinghydrocracked) distillate fuel oils and mixtures thereof. Moreover, suchfuel oils can be treated in accordance with well-known commercialmethods, such as acid or caustic treatment, dehydrogenation,hydrotreating, solvent refining, clay treatment and the like.

Particularly contemplated among the distillate fuels are Nos. 1, 2 and 3fuel oils used in heating and as diesel fuel oils, low sulfur dieselfuel, low aromatic diesel fuel, gasoline, turbine fuels, kerosene, jetcombustion fuels and mixtures thereof.

Liquid oxygenated fuels may contain alcohols, ethers, and/or gasoline inamounts of 0 to 90 volume percent alcohol or ether in gasoline. Anexample of a fuel with a high alcohol concentration is M-85, 85%methanol and 15% gasoline. The fuel may be an alcohol-type fuelcontaining little or no hydrocarbon. Typical of such fuels are methanol,ethanol and mixtures of methanol and ethanol. The fuels which may betreated with the additive include gasohols which my be formed by mixing90 to 95 volume percent gasoline with 5-10 volume percent of ethanol ormethanol. A typical gasohol may contain 90 volume percent gasoline and10 volume percent absolute ethanol. As mentioned above, oxygenated fuelsmay be made of a blend of gasoline and an ether. A typical blend ofgasoline with methyl tert-butyl ether might include 85 volume percentgasoline and 15 volume percent ether.

The fuel compositions of the instant invention may additionally compriseany of the additives generally employed in fuel compositions. Thus,compositions of the instant invention may also contain conventionalcarburetor, fuel injector, and other detergents, anti-knock compoundssuch as tetraethyl lead, anti-icing additives, upper cylinder and fuelpump lubricity additives, corrosion inhibitors, dyes, pour pointimprovers, antioxidants, cetane improvers and the like.

EXAMPLE 1 Tolyltriazole-Oleyl Amine

Approximately 80 grams (0.6 mole) tolyltriazole (Sherwin Williams Co.),167 grams (0.6 mole) oleyl amine (Armak-O, Armak Chemical Co.), 100 mlethanol, and 100 ml toluene were charged to a 1 liter flask equippedwith an agitator, Dean-Stark apparatus and dropping funnel. This mixturewas stirred to a homogeneous mixture. Glyoxal (43.5 grams, 0.3 mole, 40%in water) was added dropwise and then stirred at room temperature for 12hours. Water was then azeotropically removed by heating to 115° C. Thedark brown product (261 grams) was isolated by filtration and removal ofsolvent under reduced pressure.

EXAMPLE 2 Tolyltriazole-N-oleyl-1,3-diaminopropane

Approximately 66.6 grams (0.5 mole) tolyltriazole, 175 grams (0.5 mole)N-oleyl-1,3-diaminopropane (Armak Chemical Co.), 100 ml ethanol, and 100ml toluene were charged to a 1 liter flask equipped with an agitator,Dean-Stark apparatus, and dropping funnel. This mixture was stirred to ahomogeneous mixture. Glyoxal (36.3 grams, 0.25 mole, 40% in water) wasadded dropwise and then stirred at room temperature for 12 hours. Waterwas then azeotropically removed by heating to 150° C. The orange product(237 grams) was isolated by filtration and removal of solvent underreduced pressure.

EXAMPLE 3 Tolyltriazole-Oleyl Amine-Oleic Acid

Approximately 53 grams (0.4 mole) tolyltriazole, 111 grams (0.4 mole)oleyl amine, 100 ml ethanol, and 100 ml toluene were charged to a 1liter flask equipped with an agitator, Dean-Stark apparatus, anddropping funnel. This mixture was stirred to a homogeneous mixture.Glyoxal (29 grams, 0.2 mole, 40% in water) was added dropwise and thenstirred at room temperature for 12 hours. Water was then azeotropicallyremoved by heating to reflux temperatures of approximately 100°-120° C.While maintaining a temperature of less than or equal to 60° C., 56grams (0.2 mole) oleic acid was added slowly. The reaction mixture wasstirred at 60° C. for 1 hour. The orange product (243 grams) wasisolated by filtration and removal of solvent under reduced pressure.

EXAMPLE 4 Tolyltriazole-N-oleyl-1,3-diaminopropane-Oleic Acid

Approximately 53 grams (0.4 mole) tolyltriazole, 140 grams (0.4 mole)N-oleyl-1,3-diaminopropane, 100 ml ethanol, and 100 ml toluene werecharged to a 1 liter flask equipped with an agitator, Dean-Starkapparatus, and dropping funnel. This mixture was stirred to ahomogeneous mixture. Glyoxal (29 grams, 0.2 mole, 40% in water) wasadded dropwise and then stirred at room temperature for 12 hours. Waterwas then azeotropically removed by heating to reflux temperatures ofapproximately 100°-120° C. After cooling to less than 60° C., 112 grams(0.4 mole) oleic acid was added slowly. The reaction mixture was stirredat 60° C. for 1 hour. The orange product (310 grams) was isolated byfiltration and removal of solvent under reduced pressure.

EVALUATION OF PRODUCTS

The products of Examples 1-4 were blended into lubricants and evaluatedfor friction reduction activity using a Low Velocity Friction Apparatus(LVFA). The products of the examples were also blended into lubricantsand into distillate fuels and were tested using the Four Ball Wear Test.The conditions of the tests are described below. The results of the LVFAtests are shown in Table 1, and the results of the Four Ball wear testsare shown in Table 2 and in Table 3. In the test using the Low VelocityFriction Apparatus (LVFA), two percent of the additive produced in eachof the examples was dissolved in a standard mineral oil reference fluidblended with a dispersant/detergent/inhibitor performance packagetypical of an SG lube. Although evaluation of additives was performed inlubricant formulations, these results correlate well with expectedfrictional and fuel economy improvements when these same additives areused in fuels burned in internal combustion engines. For example, thistest predicts the reduction in friction of the piston rings movingagainst the cylinder walls that have been wetted by fuel containing theadditive. The resulting reduction in friction observed, if any, maytranslate into an improvement in economy of the fuel actually consumed.Additionally, these additives, when used in fuels, may actually helpreduce wear of the internal combustion engine parts.

The Low Velocity Friction Apparatus (LVFA) is used to measure thecoefficient of friction of test lubricants under various loads,temperatures, and sliding speeds. The LVFA consists of a flat SAE 1020steel surface (diameter 1.5 in.) which is attached to a drive shaft androtated over a stationary, raised, narrow ringed SAE 1020 steel surface(area 0.08 in.²). Both surfaces are submerged in the test lubricant.Friction between the steel surfaces is measured as a function of thesliding speed at a lubricant temperature of 250° F. The friction betweenthe rubbing surfaces is measured using a torque arm-strain gauge system.The strain gauge output, which is calibrated to be equal to thecoefficient of friction, is fed to the Y axis of an X-Y plotter. Thespeed signal from the tachometer-generator is fed to the X-axis. Tominimize external friction, the piston is supported by an air bearing.The normal force loading the rubbing surfaces is regulated by airpressure on the bottom of the piston. The drive system consists of aninfinitely variable-speed hydraulic transmission driven by a 1/2 HPelectric motor. To vary the sliding speed, the output speed of thetransmission is regulated by a lever-cam motor arrangement.

The rubbing surfaces and 12-13 ml of test lubricant were placed on theLVFA. Coefficients of friction (U_(k)) were measured at 32-58 psi over arange of sliding speeds (0 to 30 ft./min.) at room temperature and at250° F. Reported are results at 250° F., 48 psi., and at a sliding speedof zero ft./min. (static) and from the average of sliding speeds of 5and 30 ft./min. (dynamic). The data are calculated as percent decreasein friction according to: ##EQU1##

The percent change in the coefficients of friction of the test oilcontaining the example products relative to the test oil without exampleproducts is reported in Table 1. The value for the oil alone would bezero for the form of the data shown in the table.

                  TABLE 1                                                         ______________________________________                                        Friction Reducing Properties                                                  Friction Test Results Using Low Velocity Friction Apparatus                               % Reduction in Coefficient of Friction                            Test Sample   Static       Dynamic                                            ______________________________________                                        Base oil      --           --                                                 Example 1 in base oil                                                                       36           21                                                 Example 2 in base oil                                                                       34           25                                                 Example 3 in base oil                                                                       62           37                                                 Example 4 in base oil                                                                       66           41                                                 ______________________________________                                    

In the evaluation of antiwear activity associated with the additives ofthis invention combined with a distillate fuel base using the Four Ballwear test, the product of each of Examples 1 through 4 was blended intoa low sulfur distillate fuel at 0.1 wt. % additive in the fuel. Theresults of the test are shown in Table 2.

In the Four Ball Wear Test, three stationary balls are placed in alubricant cup and a lubricant containing the compound to be tested isadded thereto, and a fourth ball is placed in a chuck mounted on adevice which can be used to spin the ball at known speeds and loads. Thedistillate fuel based test samples were tested using half inch stainlesssteel balls of 52100 steel for thirty minutes under 10 kg load at 600rpm and 122° F. The test is generally as described in ASTM test methodD-2266.

K (as reported in Table 2 and in Table 3), the wear coefficient, iscalculated from the wear volume, V, of the stationary balls. The wearvolume is calculated from the wear scar diameter D in mm as follows:

    V=(15.5 D.sup.3 -0.0103L)D×10.sup.-3 mm.sup.3

where L is the machine load in kg. This equation considers the elasticdeformation of the steel balls.

WEAR COEFFICIENT K

Dimensionless K is defined as ##EQU2## where V=wear volume, mm³

H=hardness 725 kg/mm² for 52100 steel

d=(23.3 mm/rev) * (RPM) * (Time, min)

W=(0.408) * (Load in kg)

                  TABLE 2                                                         ______________________________________                                        Wear Reducing Properties                                                      Four Ball Wear Test                                                           1/2" Balls, 52100 Steel, 10 Kg., 600 RPM, 122° F., 30 min.             Test Sample       K Factor                                                    ______________________________________                                        Base fuel         38.4                                                        Example 1 in base fuel                                                                          1.0                                                         Example 2 in base fuel                                                                          1.3                                                         Example 3 in base fuel                                                                          2.9                                                         Example 4 in base fuel                                                                          3.9                                                         ______________________________________                                    

In the evaluation of antiwear activity using the Four Ball wear test onthe additives of this invention combined with a lubricant base, theproduct of each of Examples 1 through 4 was blended into a mineral baseoil at 1 wt. % additive in the fuel. The lubricating oil based sampleswere tested using half inch stainless steel balls of 52100 steel forthirty minutes under 40 kg load at 1,800 rpm and 75° C. The results ofthe test are shown in Table 3. The wear coefficient, K, as definedabove, was also used for this test using the different speed and load.

                  TABLE 3                                                         ______________________________________                                        Wear Reducing Properties                                                      Four Ball Wear Test                                                           1/2" Balls, 52100 Steel, 40 Kg., 1,800 RPM, 75° C., 30 min.            Test Sample       K Factor                                                    ______________________________________                                        Base oil          200                                                         Example 1 in base oil                                                                           0.7                                                         Example 2 in base oil                                                                           0.7                                                         Example 3 in base oil                                                                           2.8                                                         Example 4 in base oil                                                                           2.3                                                         ______________________________________                                    

As shown above, the products of this invention induce an excellentreduction in friction and have excellent fuel and lubricant antiwearactivity as indicated by LVFA and Four Ball test results.

The use of additive concentrations of glyoxal coupled nitrogenheterocycles/amines, and the products of carboxylic acids and carboxylicacid generating compounds with aldehyde/ketone/glyoxal coupled nitrogenheterocycles/amines have been found to reduce friction and to providemetal antiwear protection in lubricants and fuels. These additives areexpected to significantly reduce friction, improve fuel economy, reducewear and extend engine life. These additives may also provide oxidativestability, high temperature stability, antifatigue, anticorrosion,antistaining, metal deactivation, cleanliness, extreme pressure,demulsifying, emulsifying, detergency, and dispersancy properties. Theyalso have the potential to benefit fuel and lubricant properties byreducing hydrocarbon, carbon monoxide, and NO_(x) emissions. Mildreaction conditions should translate to a relatively easy manufacturingprocess.

Obviously, many other variations and modifications of this invention aspreviously set forth may be made without departing from the spirit andscope of this invention as those skilled in the art readily understand.Such variations and modifications are considered part of this inventionand within the purview and scope of the appended claims.

What we claim is:
 1. A lubricant composition comprising a major amountof oil with viscosity suitable for use as a lubricant, grease producedtherefrom, and a minor amount of an additive comprising the reactionproduct of:(a) at least one nitrogen heterocycle; (b) at least oneamine; (c) at least one dicarbonyl compound; and optionally, (d) atleast one carboxyl compound or carboxyl generating compound.
 2. Thelubricant composition of claim 1, wherein the dicarbonyl compoundcomprises glyoxal and wherein the additive comprises the reactionproduct of the nitrogen heterocycle, the amine, the dicarbonyl, and thecarboxyl compound or the carboxyl generating compound.
 3. The lubricantcomposition according to claim 1 wherein the nitrogen heterocycle, theamine, and the dicarbonyl compound are first reacted together, and thenthe product of this reaction is post reacted with the carboxyl compoundor carboxyl generating compound to produce the reaction product ofclaim
 1. 4. The lubricant composition of claim 1 comprising selecting(a)the nitrogen heterocycle from the triazoles characterized by thefollowing structural formula: ##STR7## where R₁ is hydrogen or an alkylgroup containing 1 to 60 carbon atoms or an alkyl group containing 2 to60 carbon atoms and at least one heteroatom which is oxygen, sulfur,nitrogen, and combinations thereof; (b) the amine from an alkyl amine,an alicyclic amine, a heterocyclic amine, an aliphatic diamine, analiphatic triamine, an oxygenated amine, and mixtures thereof; (c) thedicarbonyl from a dialdehyde or a glyoxal; and (d) the carboxyl compoundfrom a carboxylic acid, carboxylic acid generating compound, or mixturesthereof.
 5. The lubricant composition of claim 4 further comprisingselecting the dicarbonyl from those with the structure:

    R.sub.2 COR.sub.3 CO

where R₂ and R₃ are independently selected from hydrogen, a linear,branched or cyclical C₁ -C₂₀₀ hydrocarbyl or hydrocarbylene or mixturethereof, and where R₂ and R₃ can additionally independently containsulfur, oxygen, nitrogen and combinations thereof.
 6. The lubricantcomposition of claim 4 further comprising selecting the alkyl amine fromthose with the structure:

    R.sub.4 NR.sub.5 R.sub.6

where R₄, R₅, and R₆ are independently selected from hydrogen, linear,branched or cyclic C₁ -C₂₀₀ hydrocarbyl or hydrocarbylene or a mixturethereof, at least one of R₄, R₅, or R₆ must be hydrogen, and where R₄,R₅, and R₆ can additionally independently contain sulfur, oxygen,nitrogen and combinations thereof.
 7. The compound of claim 4 comprisingfurther selecting the aliphatic diamine from a diamine which has thestructural formula: ##STR8## where R₇ is an alkylene group containing 10to 30 carbon atoms and R₈ is an alkylene group containing 2 to 4 carbonatoms.
 8. The lubricant composition of claim 4 comprising furtherselecting the aliphatic triamine from a triamine which has thestructural formula:

    R.sub.9 NH(CH.sub.2 CH.sub.2 CH.sub.2)NH(CH.sub.2 CH.sub.2 CH.sub.2)NH.sub.2

where R₉ is selected from hydrogen or C₁ -C₂₀ linear, branched, orcyclic hydrocarbyl or hydrocarbylene group, and where R₉ canadditionally contain sulfur, oxygen, nitrogen and combinations thereof.9. The lubricant composition of claim 4 wherein the amine is an alkylamine having the structure:

    R.sub.10 NR.sub.11 (CH.sub.2 CH.sub.2 CH.sub.2 NH).sub.x CH.sub.2 CH.sub.2 CH.sub.2 NR.sub.12 R.sub.13

where x is 0 to 10, and R₁₀, R₁₁, R₁₂, and R₁₃ are independentlyselected from hydrogen, C₁ -C₂₀₀ linear, branched or cyclic hydrocarbylor hydrocarbylene, and where R₁₀, R₁₁, R₁₂, and R₁₃ can additionallyindependently contain sulfur, oxygen, nitrogen and combinations thereof.10. The lubricant composition of claim 4 in which the selected from thegroup consisting of pentylamine, hexylamine, octylamine, dioctylamine,dicocoamine, dioleylamine, 2-ethylhexylamine, isopropylamine,isobutylamine, diisobutylamine, bis(2-ethylhexyl)amine,1,4-diaminocyclohexane, dicyclohexylamine, hexamethyleneimine orpiperidine, morpholine, aminopropylmorpholine or aminoethylpiperazine,N-tallow-1,3-propylenediamine, N-oleyl-1,3-propylenediamine,N-linoleyl-1,3-propylenediamine, N-stearyl-1,3-propylenediamine,N-soya-1,3-propylenediamine, N-cocoyl-1,3-diaminopropane,N-oleyl-1,3-diaminopropane, N-isostearyl-1,3-propylenediamine,N-tallow-1,2-ethylenediamine, N-oleyl-1,2-ethylenediamine,N-linoleyl-1,2-ethylenediamine, N-stearyl-1,2-ethylenediamine,N-soya-1,2-ethylenediamine, N-cocoyl-1,2-diaminoethane,N-oleyl-1,2-diaminoethane, N-isostearyl-1,2-ethylenediamine, diethylenetriamine or triamino propane, N,N'-di(2-aminoethyl)-amine,bis(hexamethylene) triamine, pentamethyl diethylenetriamine,2,2-dimethyl-diethylenetriamine, N1-tert. butyl-1,2,3-triaminopropane,2,2,5,5-tetramethyl diethylenetriamine, 1,3,6-triaminomethylhexane,1,2,3-triaminoethylpropane, 4-aminomethyl-octamethylenediamine,3,3'-diamino-dipropylamine, spermidine, 4,4'-diamino-dibutylamine,6,6'diaminohexylamine, 2,4-bis(4-aminocyclohexylmethyl)cyclohexylamine,and mixtures thereof.
 11. The lubricant composition of claim 4 in whichthe amine is an oxygenated amine selected from the group consistingof(a) 3-methoxypropylamine, 3-ethoxypropylamine, 3-propyloxypropylamine,3-butyloxypropylamine, 3-octyloxypropylamine, 3-hexoxypropylamine,3-heptoxypropylamine, 3-nonyloxypropylamine or 3-decyloxypropylamine;(b) an ether diamine having the structural formula ##STR9## where a is 1to 20 and where R₁₄ is an alkyl group containing 4 to 20 carbon atoms,R₁₅ is an alkyl group containing 2 to 4 carbon atoms and R₁₆ is an alkylgroup containing 2 to 10 carbon atoms; (c) a polyether primary aminehaving the structure

    R.sub.17 --O--(C.sub.2 H.sub.3 (R.sub.18)O).sub.n --(C.sub.3 H.sub.6)--NH.sub.2

where R₁₇ is an alkyl-substituted phenyl group containing 14 to 26carbon atoms, C₆ to C₃₀ alkyl group or C₇ to C₃₀ aralkyl group, n is aninteger ranging from 2 to 10, and R₁₈ is independently an hydrogen atomor a methyl group; and (d) an hydroxyl-containing amine having thestructure ##STR10## where x and y are integers from 1 to 10 and the sumof x+y is at least 1 and R₁₉ is selected from hydrogen or C₁ -C₂₀₀linear, branched, or cyclic hydrocarbyl or hydrocarbylene group, andwhere R₂₀ and R₂₁ are independently selected from C₂ -C₁₀ hydrocarbyleneoxide, and where R₁₉ can additionally contain at least one heteroatomwhich can be oxygen, sulfur, nitrogen and combinations thereof.
 12. Thelubricant composition of claim 4 in which the amine is an oxygenatedamine selected from the group consisting ofhexoxypropyl-1,3-propylenediamine, heptoxypropyl-1,3-propylenediamine,octoxypropyl-1,3-propylenediamine, nonyloxypropyl-1,3-propylenediamineand mixtures thereof.
 13. The lubricant composition of claim 4 furthercomprising selecting the carboxylic acid from those with the structure:##STR11## where R₂₂, is selected from hydrogen, C₁ -C₃₀ linear, branchedor cyclic hydrocarbyl or hydrocarbylene or a mixture thereof, and whereR₂₂ can additionally contain sulfur, oxygen, nitrogen or a combinationthereof.
 14. The lubricant composition of claim 4 wherein the nitrogenheterocycle consists essentially of tolyltriazole; the amine is selectedfrom the group consisting of oleyl amine, N-oleyl-1,3,-diamino propane,and combinations thereof; the dicarbonyl compound consists essentiallyof glyoxal; and the carboxyl compound consists essentially of oleicacid.
 15. A lubricant composition comprising a major amount of oil withviscosity suitable for use as a lubricant or grease produced therefromand a minor amount of an additive comprising a reaction product of:(a)at least one nitrogen heterocycle comprising tolyltriazole; (b) at leastone amine selected from the group consisting of oleyl amine,N-oleyl-1,3,-diamino propane, and combinations thereof; and (c) glyoxal.16. A method of making a lubricant comprising blending a major amount ofoil with viscosity suitable for use as a lubricant or grease producedtherefrom and a minor amount of an additive comprising a reactionproduct of:(a) at least one nitrogen heterocycle; (b) at least oneamine; (c) glyoxal.
 17. A method of making a lubricant comprisingblending a major amount of oil with viscosity suitable for use as alubricant or grease produced therefrom and a minor amount of an additivecomprising a reaction product of:(a) at least one nitrogen heterocycle;(b) at least one amine; (c) at least one dicarbonyl compound; andoptionally, (d) at least one carboxyl compound or carboxyl generatingcompound.
 18. The method according to claim 17 wherein the additivecomprises the reaction product of the nitrogen heterocycle, the amine,the dicarbonyl compound and the carboxyl compound.
 19. The methodaccording to claim 17 wherein the nitrogen heterocycle, the amine, andthe dicarbonyl compound are first reacted together, and then the productof this reaction is post reacted with the carboxyl compound or carboxylgenerating compound to produce the reaction product of claim
 17. 20. Themethod according to claim 10 wherein the dicarbonyl comprises glyoxal.21. A lubricant composition comprising a major amount of oil withviscosity suitable for use as a lubricant, grease produced therefrom,and a minor amount of an additive comprising the reaction product of:(a)at least one nitrogen heterocycle selected from a triazolescharacterized by the following structural formula: ##STR12## where R₁ ishydrogen or an alkyl group containing 1 to 60 carbon atoms or an alkylgroup containing 2 to 60 carbon atoms and at least one heteroatom whichis oxygen, sulfur, nitrogen, and combinations thereof; (b) an oxygenatedamine selected from the group consisting of(i) 3-methoxypropylamine,3-ethoxypropylamine, 3-propyloxypropylamine, 3-butyloxypropylamine,3-octyloxypropylamine, 3-hexoxypropylamine, 3-heptoxypropylamine,3-nonyloxypropylamine, and 3-decyloxypropylamine; (ii) an ether diaminehaving the structural formula ##STR13## where a is 1 to 20 and where R₁₄is an alkyl group containing 4 to 20 carbon atoms, R₁₅ is an alkyl groupcontaining 2 to 4 carbon atoms and R₁₆ is an alkyl group containing 2 to10 carbon atoms; (iii) a polyether primary amine having the structure

    R.sub.17 --O--(C.sub.2 H.sub.3 (R.sub.18)O).sub.n --(C.sub.3 H.sub.6)--NH.sub.2

where R₁₇ is an alkyl-substituted phenyl group containing 14 to 26carbon atoms, C₆ to C₃₀ alkyl group or C₇ to C₃₀ aralkyl group, n is aninteger ranging from 2 to 10, and R₁₈ is independently an hydrogen atomor a methyl group; and (iv) an hydroxyl-containing amine having thestructure ##STR14## where x and y are integers from 1 to 10 and the sumof x+y is at least 1 and R₁₉ is selected from hydrogen or C₁ -C₂₀₀linear, branched, or cyclic hydrocarbyl or hydrocarbylene group, andwhere R₂₀ and R₂₁ are independently selected from C₂ -C₁₀ hydrocarbyleneoxide, and where R₁₉ can additionally contain at least one heteroatomwhich can be oxygen, sulfur, nitrogen and combinations thereof; (c) atleast one dicarbonyl compound selected from an aldehyde or a glyoxal;and optionally, (d) at least one carboxyl compound selected from acarboxylic acid, carboxylic acid generating compound, or mixturesthereof.
 22. The lubricant composition of claim 21 wherein theoxygenated amine is selected from the group consisting ofhexoxypropyl-1,3-propylenediamine, heptoxypropyl-1,3-propylenediamine,octoxypropyl-1,3-propylenediamine, andnonyloxypropyl-1,3-propylenediamine.